Production of assistants in the tex



Patented on. 12, 1937 2,095,8l4f

UNITED STATES PATENT OFFICE PRODUCTION OF ASSISTANTS IN THE TEX- TILE AND RELATED INDUSTRIES Heinrich Hopfi and Willi Schmidt, Ludwigshafen-on-the-Bhine, Germany, assignors to I. G. Farbenindustrie Aktiengesellschaft, Frankfort-on-the-Main, Germany No Drawing. Application April 24, 1933, Serial No. 667,611. In. Germany May 7, 1932 20 Claims. (01. 260-130) The present invention relates to the production ketones with polyhydric alcohols containing at of assistants in thetextile and related industries. least 3 hydroxyl groups, such as glycerine, sor- We have found that products which maybe bitol, or other hexitols, or by reactionv with .Grigemployed with great advantage as assistants in nards reagents" obtained from methyl, ethyl,

5 the textile and related industries, i. e. as wetting, n-propyl, or isopropyl bromide or monobromo- 5 washing, foaming, dispersing and like agents, for benzene, and subsequent decomposition of the example in the textile and leather industries can reaction products with water. The initial mabe obtained by causing a monomeric aliphatic terials may also be condensed with hydrocyanic carbonyl compound, i. e. an aliphatic aldehyde or acid by the usual methods to form the correketone, containing'more than 6 carbon atoms, to sponding hydroxy nitriles, or they may be con- 0 react with such organicsubstances that products verted with anyaldehydes or ketones containing are formed which are either directly soluble in preferably up to 9 carbon atoms, for example water or which permit the introduction of groups formaldehyde, acetaldehyde, propionaldehyde, which render them water-soluble, the said groups butyraldehyde, acetone, methyl-ethyl ketone,

being introduced when necessary. benzaldehyde, or benzophenone, into the corre- 15 As initial materials the single aldehydes and sponding ad s 0 t -a o y y ketones corresponding to the higher saturated amines, as for example mono-, diand tri-alkyland unsaturated fatty acids may be employed. olamines, are also suitable for condensation with Examples for aldehydes are lauric aldehyde, the aldehydes or ketones.

stearic aldehyde, oleic aldehyde or rlcinoleic By converting the products thus obtainable 20 aldehyde, caprylic aldehyde, caprinic aldehyde, which contain hydrogen atoms fixed to oxygen myristic aldehyde, palmitic aldehyde, Z-ethyl and/or nitrogen atoms, for example those conpr n aldehyde taming hydroxy and/or engine ggourisiwihth ethylene oxide, products are 0 nine w c are so (OH: CBPCHPCHrCH CH) uble in water. Products which are directly sol- 25 uble in water may also be obtained by causing the undecylenic aldehyde, or nonylic aldehyde, aldehydes or ketoncs to react with alcohol sulwhich may be obtainedfor example by a catalytic phonic acids, such as alpha-beta-dihydroxydehydrogenation of the corresponding alcohols. propane sulphonic acid, with para-phenylhydra- Examples of suitable ketones are heptadecyl zine sulphonic acid, or with-trlmethyldihydroxy- 30 methyl ketone, heptadecyl ethyl ketone, heptapropane ammonium salts decyl n-propyl ketone, di-heptadecyl ketone, heptadecenyl ethyl ketone, heptadecenyl methyl ketone, nonyl methyl ketone, undecyl methyl and similar compounds.

ketone, decenyl ethyl ketone, pentadecyl methyl It will be understood that the main subject 5 ketone, or laurone, which maybe obtained from matter of the present invention exists in a con the corresponding fatty acids by splitting ofl densation (without the splitting off of water), water and carbon dioxide. Instead of single such as occurs in the addition of hydrocyanic acid aldehydes or ketones, mixtures of aldehydes and or of an aldehyde, such as formaldehyde, or in 40 ketones or mixtures of different aldehydes or a condensation with the splitting off of water, 40 ketones, as for example the readily accessible such as occurs in the formation of acetals, hymixtures of aldehydes or ketones which corredrazones or oxazolidines. spond to the mixtures of fatty acids occurring in The products obtainable by the said methods nature may be employed, such as coconut oil are usually viscous liquids or solid wax-like 5 fatty acids, soya been 011 fatty acids, rape seed, bodies. L The introduction of groups rendering the cotton seed or linseed oil fatty acids, train oil productssoluble in water may be effected in all fatty acids or montanic acids. For example, the cases, for example by treatment with a sulphor mixture of ketones obtainable from coconut oil nating agent, such as sulphuric acid of from 80 to fatty acids and acetic acid may be employed with 100 per cent strength, fuming sulphuric acid,

v a e chlorsulphonic acid, phosphoric acid, or ethylene '50 The conversion of the initial materials into oxide. Products are always obtained which foam products which are directly soluble-in water or very strongly in aqueous solution, which have which permit of the introduction of groups rena high wetting, washing and dispersing power dering them soluble in Water may be carried out and which are capable. of employment in an r example y ndensing the aldehy es or advantageous manner for example as assist- 55 ants tor the textile and related industries The following examples will further illustrate l the nature or this invention but the invention is not restrictedto these examples. The parts are I by weight.

Example 1 184 parts cf lauric aldehyde, obtainable by the with an aqueous solution of sodium carbonate. After d y n the clear, slightly yellow liquid with dry potash, it is sub- -3ected' to distillation in vacuo; whereby the main millimetres me cury gauge) 'tion has a hydroxyl value of, 215 and consists hyde corresponding to'the formula I ,chlors'ulphonic acid, an,

wettin g'andgwashing action.

'0. at a pressure, of

part distils at about 190 The main frac-- presumably of the glycerine acetal; otlauric alde I By [treatine as been 5 thus obtained with; I acid sulphuric ester is, i

of which roams very: I

obtained. the; sodium salt strongly in aqueous solution and has excellent- Phosphoric acid or it is to be noted that the whole number a: may

Example 2 184 parts of lauric aldehyde obtainable by the catalytic dehydrogenation of dodecyl alcohol and still containing about per cent of dodecyl alcohol, and 880 parts of ethylene oxide are heated with 10 parts of nickel sulphate as a catalyst in a stirring autoclave at from 150 to 170 C. for 12 hours. A pale colored liquid is obtained which dissolves in water, giving a clear solution which has a good foaming power and which has excellent wetting power.

Example 3 300 parts of oleic aldehyde, 150 parts of glycerine and 1 part of concentrated hydrochloric acid areintimately stirred for '7 hours at from 150 to 200 C. After cooling, the mass is diluted with an equalvolume of ethyl ether and the remainders of glycerine separating out are drawn off; the solution is then washed out with an aqueous solution of common salt, dried with potash and freed from the ethyl ether by distillation. In a subsequent distillation at 2 millimetres of mercury 250 parts are distilled off at Irom 200 to 220 C.; the hydroxyl value of this main fraction is 164, the bodycontained therein corresponding'presumably to the formma:

I I /,0-CH1 The yellowish'oil thus obtained is sulphonated in I, I

the usual manner and'yieldsan excellent wetting I andwashing'agent. The product is subjected to sulphonation' with a quantity of chlorsulphonic I I I acid correspondingto thehydroxyl value- The I I, aqueous'solution iofthesodium salt, of the re- I suiting product shows good foaming :and wetting I effects.

22 parts of lauric' aldehyde are addedto a solu-I I I I I I tion' of '22 parts of: paraphenylhyd'razine sul- 2 I I phonic acid in partsoi an aqueous caustic soda I I I I I solution containing such a quantityoi caustic I, soda that the sulphonic acid is dissolved; While stirring, an aqueous normal hydrochloric acid, solution is added until the alkaline reactionto litmusdisappea-rs- I Byheating ,for 2 hours to about95 C. ,'a'to 8h. ropyoil is obtained which is easily soluble in water, in dilute aqueous solu- I ethylene oxidem aybeemployedinsteadofchlorr' I f l I I sulphonicacid andin'this case products-having I I I 'Q s r b a n d-i T m c i n I with ethylene -"oxlde proceeds according to the iisnot'precipitatedironi its aqueoussolutions by I I I I I following scheme I I calciumormagnesiumsaits.- I I In wetting out cotton, aqueous solutions of the following concentrations efiect complete wetting.

' Grains of hydra zone per litre At 70 C.

Example '5 'A "Grignarrr compound is prepared irom 40 parts of magnesium shavings, 1000 parts of ethyl ether and 164 parts of ethyl bromide. 148 parts of lauric aldehyde dispersed in 500 parts of ethyl ether are introduced into the said mixture, the magnesium compound then being decomposed therein with the aid of cold, aqueous sulphuric acid. The resulting ethereal solution is washed with water and dried with potassium carbonate. After removal oi the ether by distillation, from 96 to 97 per cent by weight of the product is obtained in a subsequent distillation at 16 millimetres of mercury at from 150 to 156 C. 105 parts of the undecyl ethyl carbinol obtained are mixed at about room temperature with parts of 98 per cent chlorsulphonic acid dissolved in 90 parts of diethyl ether. The product obtained, after neutralization with aqueous caustic soda solution, is an eifdcient wetting agent.

Ewample 6 560 parts of caustic potash are dissolved in 5000 parts of methyl alcohol. While intimately stirring, an intimate mixture of 920 parts of lauric aldehyde and 2000 parts of an aqueous 40 per cent solution of formaldehyde are slowly introduced, the mixture becoming .warm by the reaction. The clear reaction mixture is then warmed for 1 hour to about C. While passing through carbon dioxide, the methyl alcohol and the main portion of water are distilled oil, a lower layer of salt, a supernatant aqueous layer and a supernatant oily layer thus being formed. The oily layer is dissolved in a little ethyl ether, separated from the other layers and washed four times with an equal volume of water, and then dried with potassium carbonate and the ether is removed by distillation in vacuo at C. The resulting slightly colored oil has a hydroxyl value of 423 from which the body obtained may be assumed to correspond to the formula This product is probably formed in the following manner 1 o H an C a( 2)w-C The latter aldol-like compound reacts with form aldehyde, the aldehyde group of the aldol-lilre compound being reduced to the grouping -CH2OH and one molecule of CHzO being added on to the carbon atom which bears the said aldehyde group so that the-H-atom marked is replaced by CHZOH. 132 parts of the oil are dissolved in 175 parts of ethyl ether and, while stirring at from 10 to 20 C., a solution of parts of chlorsulphonic acid in 1'75 parts of ethyl other is added. After the reaction the whole is neutralized while cooling with about 225 parts, of an aqueous 30 per cent caustic soda solution and the ether and water are distilled off in vacuo. The yield is about 390 parts. The aqueous/solution of the resulting sodium salt of the acid sulphuric ester has a very high wetting power.

Example 7 270 parts of 79 per cent commercial ethylene diamine are slowly added to 610 parts of lauric aldehyde. The mixture is incorporated with 5 per cent of its weight of cobalt prepared from basic cobalt carbonate by heating in a current oihydrogen to 325 C. The whole is then heated in a stirring autoclave for 5 hours to 230 C. at a pressure of hydrogen of 180 atmospheres. The reaction product is then freed from the cobalt by filtration at from 50 to 100 C. and distilled at 15 millimetres of mercury. The main quantity of the resulting product boils between and 200 C. Aqueous solutions of said fraction may find useful application for fixing substantive dyestuffs on cotton or artificial silk such as viscose.

The hydrochloric salt of the product is rather diiiicultly soluble in water but its solution has a high foaming and wetting power. The wetting power of the product may still be increased by interaction of lauric aldehyde and ethylene diamine, said product being condensed with ethylene oxide.

4. The process of producing assistants in the textile and related industries which comprises reacting a monomeric, aliphatic carbonyl com pound containing directly attached to the carbonyl group at least one aliphatic hydrocarbon radicle with at least 6 carbon atoms, with an organic substance containing at least one basic nitrogen atom and at least two reactive hydrogen atoms attached to nitrogen not directly attached to a nucleus, the said organic substance containing up to 6 carbon atoms and a grouping adapted for applying water-solubility to the final product, and introducing a water-solubilizing group by way of the radicle of the later substance.

textile and related industries which comprises reacting a monomeric, aliphatic carbonyl compound containing directly attached to the carbonyl group at least one aliphatic hydrocarbon radicle with at least 6 carbon atoms, with a primary aliphatic amine containing besides the amino group a further amino group, and introducing a water-solubilizing group by way of the radicle' oi the latter substance.

6. The process oi producing assist nts in the textile and related industries whic comprises reacting a monomeric, aliphatic carbonyl compound containing directly attached to the car bonyl group at least one aliphatic hydrocarbon radicle with at least 6 carbon atoms, with an aliphatic, primary diamine, and introducing a water-solubllizing group by way of the radicle of the said diamine.

7. The process of producing assistants in the textile and related industries which comprises reacting a monomeric, aliphatic carbonyl compound containing directly attached to the carbonyl group at least one aliphatic hydrocarbon 5. The process of producing assistants in the radicle with at least 6 carbon atoms, with ethylene I (wherein X stands for an aliphatic hydrocarbon radici, .5 stands for a member of the group consisting of hydrogen and an aliphatic hydro- 1 carbon radicle and wherein the sum of the car-- bon atoms contained in X and Y is at least 6) to react with a compound (wherein Z is an organic radicle containing up to 6 carbon atoms, a grouping adapted for applying water-solubility to the final product and at least the two hydrogen atoms shown in amino groups not directly attached to a nucleus) to (wherein X stands for an aliphatic hydrocarbon radicle, Y stands for a member of the group consisting of hydrogen and an aliphatic hydrocarbon radicle and wherein the sum of the carbon atoms contained in X and Y is at least 6) to react with a compound (wherein Z is an organic radicle with up to 6 carbon atoms containing a water-solubilizing group and containing at least the two hydrogen atoms shown in amino groups not directly attached to a nucleus) to form a compound corresponding to the formula (wherein the two linkages between C and Z shown do not necessarily originate from the same atom of Z).

10. The process of producing assistants in the textile and related industries which comprises causing a monomeric aliphatic compound corresponding to the formula (wherein X stands for an aliphatic hydrocarbon radicle, Y stands for a member of-the group consisting of hydrogen and an aliphatic hydrocarbon radicle and wherein the sum of the carbon atoms contained in X and Y is at least 6) to re act with a compound (wherein Z is an organic radicle with up to 6 carbon atoms containing at least the two hydrogen atoms shown in amino groups not directly attached to a nucleus) to form a compound corresponding to the formula XCY z (wherein the two linkages between C and Z shown do not necessarily originate from the same atom of Z) and introducing a water-solubilizing igroup into a hydroxyl or amino group contained 11. The process of producing assistants in the textile and related industries which comprises causing a monomeric aliphatic compound corresponding to the formula.

(wherein X stands for an aliphatic hydrocarbon radicle, Y stands for a member of the group consisting of hydrogen and an aliphatic hydrocarbon radicle and wherein the sum of the carbon atoms contained in X and Y is at least 6) to react with a compound (wherein Z is an aliphatic radicle containing at least the two hydrogen atoms shown in amino groups) to form a compound corresponding to the formula (wherein the two linkages between C and Z shown do not necessarily originate from the same atom of Z), and introducing a water-solubilizing group into Z at any time.

12. The process of producing assistants in the textile and, related industries which comprises causing a monomeric aliphatic compound corresponding to the formula (wherein X stands for an aliphatic hydrocarbon radicle, Y stands for a member of the group consisting of hydrogen and an aliphatic hydrocarbon radicle and wherein the sum of the carbon atoms contained in X and Y is at least 6) to react with a compound (wherein Z is an aliphatic radicle containing a water-solubilizing group and containing at least the two hydrogen atoms shown in amino groups) to form a compound corresponding to the formula X-CY (wherein the two linkages between C and Z shown do not necessarily originate from the same atom of Z).

13. The process of producing assistants in the textile and related industries which comprises causing a monomeric aliphaticcompound corresponding to the formula (wherein X stands for an aliphatic hydrocarbon radicle, Y stands for a member of the group consi'sting of hydrogen and an aliphatic hydrocarbon radicle and wherein the sum of the carbon atoms'contained in X and Y is atleast 6) to react with a compound 'monomeric aliphatic carbonyl compound corresponding to the formula X--CY (wherein the two linkages between C and Z shown from the same atom an aliphatic hydrodo not necessarily'originate of Z) wherein X stands for carbon radicle, Y group consisting of hydrogen and an aliphatic hydrocarbon radicle, wherein the sum of the carbon atoms contained in X and Y is at least 6 wherein Z is an organic radicle up to 6 carbon atoms attached to the C-atom shown by means of two linkages each of which originates from a nitrogen atom not directly attached to a nucleus and wherein A stands for a water-solubilizing group.

15. A water-soluble conversion product of a monomeric aliphatic aldehyde corresponding to the formula (wherein the-two linkages between C and Z shown do not necessarily originate from the same atom of Z), wherein X stands for an aliphatic hydrocarbon radicle containing at least 6 carbon atoms, wherein z is an organic radicle up to 6 carbon atoms attached to the C-atom shown by means of two linkages eachof which originates from a nitrogen atom not directly attached to a nucleus and wherein A stands for a water-solubilizing group.

16. A water-soluble conversion product of lauric aldehyde corresponding to the formula (wherein the two linkages between C and Z shown do not necessarily originate from the same atom of Z), wherein X is the hydrocarbon radicle 0 of lauric aldehyde, wherein Z is an organic radicle -monomeric aliphatic carbonyl stands for a member of the.

- shown do not necessarily of lauric aldehyde,

- of two linkages each of tached to a nucleus, and wherein A stands for a water solubilizing group.

17. A water-soluble conversion product 01' a compound corresponding to the formula x-c-y A (wherein the two linkages between C and Z shown do not necessarily originate from the same atom of Z), wherein X stands for an aliphatic hydrocarbon radicle, Y stands for a member of the group consisting of hydrogen and an aliphatic hydrocarbon radicle, wherein the sum 01' the carbon atoms contained in X and Y is at least 6, wherein Z is an aliphatic radicle attached to the C-atom shown by means of two linkages each of which originates from a nitrogen atom and wherein A stands for a water-soiubilizing group.

18. A water-soluble conversion product of a monomeric aliphatic aldehyde corresponding to the formula x-g-H (wherein the two linkages between C and 2 shown do not necessarily originate from the same atom of Z) wherein X stands for an aliphatic hydrocarbon radicle containing at least 6 carbon atoms, wherein Z is an aliphatic radicle attached to the C-atom shown by means of two linkages each of which originates from a nitrogen atom and wherein A stands for a water-solubilizing roup.

19. A water-soluble conversion product or lauric aldehyde corresponding to the formula XCH z-s (wherein the two linkages between C and Z originate from the same atom of Z) wherein X is the hydrocarbon radicle wherein Z is an aliphatic radicle attached to the C-atom shown by means which originates from a nitrogen atom and wherein A stands for a water-solubilizinggroup.

20. The process of producing assistants in the textile and related industries which comprises reacting a monomeric aliphatic carbonyl compound containing directly attached to the carbonyl group at least one aliphatic hydrocarbon radicle with at least 6 carbon atoms, with an aliphatic substance containing up to 6 carbon atoms, a grouping adapted for applying water-solubility to the final product, at least one basic nitrogen atom and at least two reactive hydrogen atoms attached to nitrogen which is not directly attached to a nucleus, and introducing a watersolubilizing group by way of the radicle of the latter substance.

HEINRICH HOPFF. WILL; SCHLEUI. 

